WO2017129231A1 - Procédé de filage au mouillé pour la production d'une fibre contenant de la lignine utilisée comme précurseur pour une fibre de carbone - Google Patents

Procédé de filage au mouillé pour la production d'une fibre contenant de la lignine utilisée comme précurseur pour une fibre de carbone Download PDF

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Publication number
WO2017129231A1
WO2017129231A1 PCT/EP2016/051589 EP2016051589W WO2017129231A1 WO 2017129231 A1 WO2017129231 A1 WO 2017129231A1 EP 2016051589 W EP2016051589 W EP 2016051589W WO 2017129231 A1 WO2017129231 A1 WO 2017129231A1
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WIPO (PCT)
Prior art keywords
lignin
fiber
carbon
precursor
precursor fiber
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PCT/EP2016/051589
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German (de)
English (en)
Inventor
Johannes Ganster
André Lehmann
Robert Protz
Jens Erdmann
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
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Application filed by Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority to EP16702897.6A priority Critical patent/EP3408433A1/fr
Priority to US16/072,514 priority patent/US20190032250A1/en
Priority to PCT/EP2016/051589 priority patent/WO2017129231A1/fr
Priority to JP2018538736A priority patent/JP2019502839A/ja
Publication of WO2017129231A1 publication Critical patent/WO2017129231A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate

Definitions

  • the invention relates to a method for producing a Precursormaschine which is suitable for further processing to carbon and activated carbon fibers.
  • the process is a wet spinning process in which a spinning solution of lignin or lignin derivatives, cellulose carbamate and caustic is pressed through the holes of a nozzle and introduced directly into a coagulation bath.
  • the precursor fiber precipitating in the bath can be subjected to various further process steps: it can be drawn, post-treated, dried at elevated temperature and wound up. Since it is a low cost starting material, it can subsequently be used to make carbon and activated carbon fibers.
  • Carbon fibers are high-performance reinforcing fibers that have long been used for composite materials in aircraft construction, high-performance vehicle construction (Formula I, high-performance sailing vessels, etc.), used for sports equipment and wind turbines.
  • One current challenge is to produce medium-quality carbon fibers with low production costs so that they can also be used in the automotive industry.
  • the main driving force for this is the goal to provide electric vehicles, which have a low weight, but nevertheless a stable body.
  • Carbon fibers are produced by heat treatment of organic precursor fibers at temperatures above 1000 ° C.
  • Precursors were prepared according to the method described by C.E. Ford and C.V. Mitchell developed and patented continuous processes (US 3,107,152).
  • the carbon fibers produced in this way were first marketed under the trade name "Thornel 25" with strengths of 1.25 GPa and moduli of 172 GPa, and further developments made it possible to produce further carbon fibers with improved properties, which had strengths of up to 4.0 GPa and moduli of elasticity up to 690 GPa.
  • the carbon fiber should have at least an E modulus of 170 GPa and a strength of 1.7 GPa.
  • the most intensively investigated raw material for the production of an alternative precursor for carbon fibers is the biopolymer lignin.
  • This offers the advantage of a very high carbon yield (about 60% by weight) compared to PAN (50% by weight) or cellulose (20-30% by weight).
  • Lignin is a polyaromatic polyol, which is part of the wood and is obtained in large quantities as a by-product of pulp production.
  • the chemical structure of lignin is determined by the type of wood used in the cell process and the pulping process. The majority of lignin is currently used only for energy purposes. With lignin, a very cost-effective raw material is available, which is virtually non-fiber-forming in unmodified form.
  • a process variant for producing a lignin-based precursor fiber for For example, a carbon fiber describes Kadla (JF Kadla et al., Carbon, 40, 2913-2920, 2002).
  • Kadla JF Kadla et al., Carbon, 40, 2913-2920, 2002.
  • a commercially available kraft lignin is melt-spun into a lignin fiber.
  • this process proved to be disadvantageous in that a cost-intensive thermal pretreatment of the lignin is necessary.
  • the carbon fibers made from the melt-spun, lignin-containing precursors had strengths of only about 0.4 GPa and moduli in the range of 40 to 50 GPa. They do not therefore meet the mechanical characteristics aimed at by automobile manufacturers.
  • solutions containing lignin and a fiber-forming polymer has the advantage that they are non-melting polymers from the outset. These allow for faster conversion and process steps to remove meltability are not necessary.
  • Such a process for producing a lignin-containing precursor fiber is described in US Pat. No. 3,461,082.
  • a solution of a polymer such as PAN or viscose and lignin is processed by the dry spinning process.
  • the spinning mass is conveyed through a spinneret, and the filament bundle produced then passes into a spinning shaft loaded with a hot gas medium.
  • the solvent evaporates and the Polymers are regenerated in fiber form and can be further processed.
  • viscose For the use of PAN as a fiber-forming polymer again results in a direct dependence on the price of oil.
  • the use of viscose also has disadvantages, since viscose is cellulose xanthate and this is not a storage-stable compound, since at any time xanthate substituents can be eliminated. This does not meet the quality requirements that a subsequent carbon fiber conversion process will place on the precursor material.
  • EP57105, EP178292 and EP2110468 describe a possibility Formed bodies of regenerated cellulose consist of precipitating a solution of cellulose carbamate.
  • Cellulose carbamate is formed by the reaction of cellulose with urea, is soluble in cold sodium hydroxide solution and can be regenerated in acidic, saline aqueous solutions or heated sodium hydroxide solution.
  • cellulose carbamate may also be formed from NMMO by means of air gap nippling, as in EP 1716273B1.
  • the structure formation of the regenerated fiber in this process takes place in the air gap and leads to high-modulus and high-strength fibers.
  • the stability of the cellulose carbamate spinning solution in NMMO is problematic since it leads to an increased splitting off of the carbamate substitutes, which permanently alters the rheological properties of the spinning solution and thus the spinning behavior.
  • gaseous ammonia which escapes through the spinneret and leads to spin instabilities, is produced as a cleavage product.
  • a further object of the present invention is to provide a corresponding lignin-containing precursor fiber which has high moduli of elasticity and strengths.
  • the present invention relates to the further processing of the precursor fiber into a carbon fiber and to a correspondingly produced carbon fiber or activated carbon fiber.
  • Claim 15 relates to a precursor fiber produced accordingly.
  • claim 19 indicates a method for producing a carbon fiber from the precursor fiber.
  • Claim 22 provides a correspondingly made carbon fiber and claim 24 shows uses of this carbon fiber.
  • a spinning solution containing at least one kind of lignin or lignin derivative and a cellulose carbamate and a solvent is extruded through a hole spinneret which dips into a coagulation bath , wherein the lignin-containing precursor fiber precipitates.
  • the spinning process according to the invention is thus a wet spinning process.
  • the at least one type of lignin or the lignin contained in the lignin derivative is extracted from a softwood, hardwood or annual source of plants, the lignin particularly preferably having a weight-average molar mass distribution between 500 g / mol and 20,000 g / mol, more preferably between 2000 g / mol and 10000 g / mol, very particularly preferably between 4000 g / mol and 10000 g / mol. It is likewise preferred in the process according to the invention if the lignin or lignin derivative is less than 1% by weight.
  • Contains ash This can be achieved by adding the appropriate lignin or lignin derivative is washed intensively with water or optionally with acids.
  • the cellulose carbamate has a viscosity determined by means of DP Cu oxam between 150 and 750, more preferably a DPcuoxam between 250 and 550.
  • the cellulose carbamate preferably also has a degree of substitution between 0.1 and 1.0, in particular between 0.2 and 0.6.
  • cellulose carbamate is used in a concentration of more than 6% by weight, particularly preferably more than 8% by weight, very particularly preferably more than 10% by weight, based on the spinning solution. In this way, a nitrogen content of the precursor fiber results, which advantageously has an effect on the further processing of the fiber into a carbon fiber.
  • the spinning solution has a mass ratio of cellulose carbamate to the at least one type of lignin or lignin derivative between 0.60 and 1.80, more preferably between 0.80 and 1.20, most preferably 1.00.
  • the solvent is selected from the group consisting of
  • Alkali solutions in particular sodium hydroxide or potassium hydroxide,
  • Tertiary amine oxides in particular N-methylmorpholine N-oxide
  • Ionic liquids preferably selected from the group consisting of imidazolium compounds, pyridinium compounds or tetraalkylammonium compounds, particularly preferably 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate; and or
  • the solvent consists exclusively of alkali solutions, tertiary amine oxides, in particular N-methylmorpholine N-oxide, and that the solvent contains no ionic liquids.
  • the spinning solution consists of at least one kind of lignin or lignin derivative and a cellulose carbamate and a solvent and that it contains no ionic liquids, no cellulose, no further cellulose derivatives and no other additives.
  • the spinning solution spinning aid selected from the group consisting of inorganic substances, in particular ZnO, organic additives, in particular quaternary ammonium compounds (cationic, eg Berol Spin 641), alkyl ethers of polyoxyethylene glycol (non-ionic, eg Berol Visco 32 ) or sulfonated oils (anionic), or mixtures thereof.
  • the spinning solution can be prepared by stirring or kneading the at least one kind of lignin or lignin derivative and cellulose carbamate in the solvent at a temperature of less than 5 ° C, preferably less than 0 ° C. It is stirred or kneaded until the solution is homogeneous and free of fibers.
  • the spinning solution thus produced is filtered through the hole spinneret into the coagulation bath prior to extrusion. Thus, possibly contained insoluble constituents can be separated.
  • the hole spinneret has a spinneret diameter of 50 to 500 ⁇ m, more preferably 50 to 100 ⁇ m.
  • the coagulation bath preferably has a pH of between 1 and 7, more preferably between 2 and 5.
  • the temperature of the spinning bath is preferably 5 ° C to 60 ° C, more preferably 10 to 50 ° C.
  • the coagulation bath in which the fiber precipitates after extrusion through the spinneret, preferably water and / or a solvent selected from the group of alcohols, saturated or unsaturated hydrocarbons, the polar aprotic compounds, particularly preferably DMF, DMSO, DMAc, or mixtures thereof, in particular in an amount of between 10 and 50% by volume or water, acid, more preferably sulfuric acid, and salts, more preferably selected from the group of sulphates, chlorides, salts with lithium, sodium, potassium, cesium, Ammonium, magnesium, calcium, zinc, copper, nickel, cadmium, or mixtures thereof as a cation, preferably in a concentration between 40 and 240 g / L, more preferably in a concentration between 60 and 240 g / L.
  • the composition of the coagulation bath preferably depends on the composition of the spinning solution. If the spinning solution contains polar, aprotic additives, e.g. DMSO, DMF, DMAc for viscosity control, the spinning bath is preferably composed of water and / or alcohols, saturated or unsaturated hydrocarbons, polar aprotic compounds, more preferably DMF, DMSO, DMAc, or mixtures thereof.
  • polar, aprotic additives e.g. DMSO, DMF, DMAc for viscosity control
  • the spinning bath is preferably composed of water and / or alcohols, saturated or unsaturated hydrocarbons, polar aprotic compounds, more preferably DMF, DMSO, DMAc, or mixtures thereof.
  • the spinning bath is preferably composed of water and / or sulfuric acid and salt. It is further preferred that the precipitated in a coagulation bath
  • Precursorfaser is then introduced into a stretching bath and stretched to 110 to 500%, preferably to 110 to 300%, of their length, wherein the stretching bath water, air, or a mixture of water and a solvent, preferably at a temperature of more than 60 ° C, particularly preferably at a temperature of more than 80 ° C, most preferably at a temperature of more than 100 ° C, contains or consists of the fact that the Precursormaschine washed with distilled water, dried by heated rollers and / or by a through-flow drying at a temperature between 40 and 100 ° C, preferably between 60 and 80 ° C, and / or wound up.
  • the stretching bath water, air, or a mixture of water and a solvent preferably at a temperature of more than 60 ° C, particularly preferably at a temperature of more than 80 ° C, most preferably at a temperature of more than 100 ° C, contains or consists of the fact that the Precursormaschine washed with distilled water, dried by heated rollers and /
  • the degree of structural orientation achieved by stretching the precursor fiber is unexpectedly high and contributes to the extremely good mechanical properties of the resulting carbon fiber.
  • the precursor fiber is coated with a spinning oil before and / or after it is dried.
  • the precursor fiber is in the form of an endless Mulitfilamentgarns in stabilization and this is transported continuously through an oven.
  • the Precusormaschine can be transferred at residence times between 10 to 100 minutes and oven temperatures between 100 and 350 ° C in an infusible and non-combustible state.
  • a precursor fiber is also specified for the production of carbon fibers.
  • the precursor fiber according to the invention is characterized by a content of at least one type of lignin or lignin derivative of more than 5 wt .-%, preferably more than 10 wt .-%, particularly preferably between 30 and 80 wt .-% and has one according to DIN 53834 measured strength of at least 5 cN / tex, preferably of at least 10 cN / tex, more preferably of at least 15 cN / tex, most preferably of at least 20 cN / tex, and an E modulus of at least 350 cN / tex, preferably from at least 550 cN / tex, most preferably at least 750 cN / tex.
  • the precursor fibers according to the invention surprisingly withstand very high heating rates of up to 50 ° C./min, which are used when the precursor fiber is stabilized. Besides, they are unexpected high carbon yield after carbonization to carbon fibers. Also, the looping, buckling and tensile strength, which is in the range of 150 to 200 MPa, and their elongation at break properties are remarkable and exceed the corresponding properties of comparable lignin precursor fibers of the prior art.
  • the precursor fiber according to the preceding claim preferably has a nitrogen / carbon mass ratio of less than 0.06, more preferably less than 0.04, most preferably less than 0.02.
  • the precursor has a round cross-section with a diameter of less than 70 ⁇ .
  • the precursor fiber according to the invention can be produced particularly advantageously according to a method described above.
  • a method for producing a carbon fiber in which the precursor fiber is stabilized at temperatures between 100 and 300 ° C. and simultaneously stretched in the range between 0 and 300% relative to its initial length, the precursor fiber becoming infusible and incombustible, and gets an oriented structure.
  • the stabilized, oriented Precursormaschine can be precarbonated at temperatures between 300 and 900 ° C and stretched in the range between 0 and 300% based on their initial length, wherein a carbon content of the fiber of more than 80 wt .-% and an oriented structure are obtained ,
  • the carbon fiber thus obtained can also be graphitized at temperatures of 2000-3000 ° C.
  • the present invention provides a carbon fiber comprising a lignin-containing precursor fiber which contains a carbon content of more than 80% by weight, preferably more than 90% by weight.
  • the carbon fiber according to the invention is advantageous after the previously described method for producing a carbon fiber produced.
  • the carbon fiber which was prepared according to the previously described method for producing a carbon fiber, for the production of a chemically activated carbon fiber and / or for the production of composite materials is used.
  • the carbonized or graphitized carbon fiber can be activated physically or chemically by heat treatment in an oxidizing atmosphere or plasma treatment or treatment with chemicals on the surface.
  • Example 1 250 g of cellulose carbamate ⁇ DPCuox 258, N content 2.2%, moisture content 10
  • the low-viscosity spinning solution thus produced was at a temperature of +5 ° C by means of a spinning pump to the spinneret (600 hole, 70 ⁇ ), which in a 40 ° C tempered aqueous spin bath of 80 g / l sulfuric acid and 140 g / l sodium sulfate protruded, promoted.
  • the coagulated filaments were drawn off by means of a nozzle delay of 0.7 and fed to the laundry.
  • the filaments were washed by means of 60 ° C warm distilled water and dried at 80 ° C.
  • the filaments thus produced had a strength of 19 cN / tex, an elongation of 6% and a modulus of 923 cN / tex.
  • the lignin content of the filaments was 49% by weight.
  • the multifilament yarn was subjected to the process of stabilization using temperatures in the range from 100 to 300 ° C. and reaction times at corresponding temperatures of about 80 minutes. Due to different speeds of the yarn transport devices before and after the tube furnace an elongation of the multifilament yarn of 100% was realized during the heat. In this case, the structure of the fiber material is oriented, thus significantly improving the mechanical properties of the final C fibers.
  • the resulting oriented and stabilized continuous multifilament yarn was then wound on a spool core.
  • the corresponding multifilament yarn is characterized by infusibility, incombustibility, freedom from adhesion of sufficient resistance to snagging and kinking and tensile strength of about 200 MPa and elongations at break of about 5%.
  • the process of refcarbonmaschine was carried out and applied to temperatures in the range of 300-900 ° C and exposure times at corresponding temperatures of 30 min.
  • the resulting oriented and precarbonated continuous multifilament yarn was then wound on a spool core.
  • the corresponding multifilament yarn is characterized by a carbon content> 80% by weight.
  • Example 3 300g of cellulose carbamate (DPCuox: 274, DS 0.3) are taken together with 300 g
  • Organosolv lignin with 1500 g Ethylmethylimidazoliumacetat and 500 g of dimethyl sulfoxide mixed and dissolved in a horizontal kneader at 110 ° C within 2.5 h.
  • the resulting homogeneous, black solution is completely fiber-free and has a viscosity of 65 Pa s at 50 ° C.
  • the filtered solution was pumped through pressure and gear pump through a 120- Hole spinneret (hole diameter 70 ⁇ ) in a 10 vol .-% Ethylmethylimidazoliumacetat promoted aqueous coagulation bath and precipitated.
  • the filaments were washed by means of 60 ° C warm distilled water and dried at 80 ° C.
  • the filaments thus produced had a strength of 24 cN / tex, an elongation of 8% and a modulus of 1150 cN / tex.
  • the lignin content of the filaments was 41% by weight.
  • the continuous multifilament yarn prepared by the process of Example 3 consisting of lignin and cellulose carbamate (50/50 mass%) was continuously transported through a tube furnace and heat applied. During this process step (stabilization), the multifilament yarn was exposed in the air to temperatures in the range of 100-300 ° C and exposure times at corresponding temperatures of about 80 min. However, the multifilament yarn produced according to Example 3 could only be stretched by a maximum of 10% during the exposure to heat, as a result of which the structure of the fiber material was orientated only insufficiently. After the subsequent process steps of the precarbonization and carbonization (analogously to Example 2), the mechanical properties of the final C fiber based on the multifilament yarn produced according to Example 3 were only a fraction of the level achieved with multifilament yarns from Example 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne un procédé de production d'une fibre de précurseur, qui est adaptée à être retraitée en fibres de carbone et en fibres de carbone activées. Ledit procédé est un procédé de filage au mouillé, selon lequel une solution de filage de lignine ou de dérivés de lignine, de carbamate de cellulose et de lessive alcaline est pressée à travers les trous d'une buse et directement introduite dans un bain de coagulation. La fibre de précurseur précipitée dans le bain peut être soumise à différentes étapes de procédé : elle peut être étirée, retraitée, séchée à très haute température et enroulée. Etant donné qu'elle représente une charge d'alimentation peu onéreuse, elle peut être utilisée par la suite pour la production de fibres de carbone et de fibres de carbone activées.
PCT/EP2016/051589 2016-01-26 2016-01-26 Procédé de filage au mouillé pour la production d'une fibre contenant de la lignine utilisée comme précurseur pour une fibre de carbone WO2017129231A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP16702897.6A EP3408433A1 (fr) 2016-01-26 2016-01-26 Procédé de filage au mouillé pour la production d'une fibre contenant de la lignine utilisée comme précurseur pour une fibre de carbone
US16/072,514 US20190032250A1 (en) 2016-01-26 2016-01-26 Wet spinning method for producing a lignin-containing fiber as a precursor for a carbon fiber
PCT/EP2016/051589 WO2017129231A1 (fr) 2016-01-26 2016-01-26 Procédé de filage au mouillé pour la production d'une fibre contenant de la lignine utilisée comme précurseur pour une fibre de carbone
JP2018538736A JP2019502839A (ja) 2016-01-26 2016-01-26 炭素繊維用の前駆物質としてのリグニン含有繊維を製造するための湿式紡糸方法

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PCT/EP2016/051589 WO2017129231A1 (fr) 2016-01-26 2016-01-26 Procédé de filage au mouillé pour la production d'une fibre contenant de la lignine utilisée comme précurseur pour une fibre de carbone

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WO2017129231A1 true WO2017129231A1 (fr) 2017-08-03

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EP (1) EP3408433A1 (fr)
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SE1850127A1 (en) * 2018-02-05 2019-08-06 Rise Innventia Ab Method of wet spinning precursor fibers comprising lignin and gelling hydrocolloid, and precursor fibers therefrom

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SE539261C2 (en) 2015-10-08 2017-06-07 Stora Enso Oyj A process for the manufacture of a lignin shaped body
US10633770B2 (en) 2018-01-04 2020-04-28 North Carolina State University Coagulation map for fiber spinning
GB2579864A (en) * 2018-12-18 2020-07-08 Univ Limerick Improvements relating to thermoelectric materials
DE102019004219A1 (de) * 2019-06-17 2020-12-17 Faserinstitut Bremen E.V. Precursor aus Lignin und Verfahren zur Herstellung eines Precursors aus Lignin für die Herstellung von Kohlenstofffasern
CN111663202A (zh) * 2020-06-23 2020-09-15 扬州利宏碳纤维材料有限公司 用于碳纤维丝生产的装置
CN111979611B (zh) * 2020-08-31 2023-06-23 福建工程学院 一种木质素/纳米纤维素基碳纤维及其制备方法

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EP2524980A1 (fr) * 2011-05-18 2012-11-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de fabrication de fibres de précurseur contenant de la lignine et de fibres de carbone
US20140099505A1 (en) * 2012-10-09 2014-04-10 Iowa State University Research Foundation, Inc. Compositions including esterified lignin and poly(lactic acid) and carbon fibers produced therefrom

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EP2524980A1 (fr) * 2011-05-18 2012-11-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de fabrication de fibres de précurseur contenant de la lignine et de fibres de carbone
US20140099505A1 (en) * 2012-10-09 2014-04-10 Iowa State University Research Foundation, Inc. Compositions including esterified lignin and poly(lactic acid) and carbon fibers produced therefrom

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE1850127A1 (en) * 2018-02-05 2019-08-06 Rise Innventia Ab Method of wet spinning precursor fibers comprising lignin and gelling hydrocolloid, and precursor fibers therefrom
WO2019151937A1 (fr) * 2018-02-05 2019-08-08 Rise Innventia Ab Procédé de filage humide de fibres précurseurs comprenant de la lignine et un hydrocolloïde gélifiant, et fibres précurseurs associées
SE541449C2 (en) * 2018-02-05 2019-10-08 Rise Innventia Ab Method of wet spinning precursor fibers comprising lignin and gelling hydrocolloid, and precursor fibers therefrom

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JP2019502839A (ja) 2019-01-31
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